JPH06903B2 - Black ink composition for writing - Google Patents

Description

The present invention relates to a black ink composition for writing which contains ethanol as a main solvent component. More specifically, the present invention relates to glass,
The present invention relates to a black ink composition for writing that can be written on wood products such as plastics, paper, cloth, and stones, has excellent water resistance and light resistance, and has low odor and toxicity.

[Conventional technology]

Writing ink is usually composed of water-based ink containing water and a water-soluble solvent such as polyhydric alcohol as a main solvent component, hydrocarbon,
It is roughly classified into oil-based inks that use a ketone or ester solvent as the main solvent.

The former water-based ink is slow-drying and non-water-resistant, so that it has a drawback that it is contaminated and disappears when the handwriting is wet.

The latter oil-based ink is quick-drying because it uses an organic solvent, and although the above-mentioned drawbacks of water-based ink due to the use of water can be overcome to some extent, the odor and toxicity of the solvent are considered to be a health problem. ing.

[Problems to be solved by the invention]

As described above, conventional water-based inks and oil-based inks have their respective drawbacks. An alcoholic ink composition containing a dye, an alcohol-soluble resin, and an alcohol-based solvent has hitherto been ameliorated. Various things have been proposed. (JP-A-59-41369,
JP-A-60-69172 and JP-B-62-25183. ) However, in the alcoholic ink compositions that have been proposed so far, the solubility of the dye, especially the black dye used for the black ink, is low in order to use the highly safe ethanol as the main solvent component in the alcohol solvent. However, there is a problem that it cannot be dissolved in a practically sufficient concentration, and that even if it can be dissolved, long-term stability is poor.

On the other hand, various oil-based inks which use an acid and a salt-forming dye of a direct dye and a cationic surfactant as colorants have been proposed (JP-B-38-26088, JP-B-53-3).
1044, JP-B-60-2340, JP-A-59-155
475. ), Even with these salt-forming dyes, there is a problem in that black ones have low solubility in alcoholic solvents containing ethanol as a main solvent component, and black inks having practically sufficient color density cannot be obtained. .

[Means for solving problems]

As a result of earnest research to solve such problems,
A coloring agent obtained by reacting a specific cationic surfactant with a metal-containing complex hydrochloric acid dye has excellent solubility in an alcohol solvent containing ethanol as a main solvent component, and a black ink composition for writing that further contains this coloring agent. It was found that the product has excellent water resistance and light resistance, and the present invention has been reached.

That is, the present invention provides a colorant obtained by reacting a cationic surfactant represented by the following general formula [I] with a metal complex hydrochloric acid dye described below, an alcohol-soluble resin, and an alcohol solvent containing ethanol as a main solvent component. And a black ink composition for writing.

(Wherein X is a halogen atom; R is a saturated or unsaturated aliphatic hydrocarbon group having 12 to 18 carbon atoms; and the total number of m and n is 2
Indicates an integer of -15. ) The present invention will be described in more detail below.

The colorant in the present invention can be produced by reacting a cationic surfactant represented by the general formula [I] with a metal complex hydrochloric acid dye. Examples of the cationic surfactant represented by the general formula [I] include polyoxyethylene lauryl monomethyl ammonium, polyoxyethylene myristyl monomethyl ammonium, polyoxyethylene cetyl monomethyl ammonium, polyoxyethylene stearyl monomethyl ammonium, polyoxyethylene oleyl monomethyl ammonium. Examples of the halide include chloride, bromide, iodide, and the like, but it is not always necessary to use pure products such as natural coconut oil, beef tallow, and petroleum-decomposed olefins. A polyoxyethylene alkylmonomethyl ammonium halide derived from may be used.

Examples of the metal complex hydrochloric acid dye that is reacted with these cationic surfactants include CI Acid Black 52, CI Acid Black 52: 1, CI Acid Black 107, C.I.
I. Acid Black 118, CI Acid Black 11
9, CI Acid Black 155 and the like can be mentioned, but particularly when used as a coloring agent, it has excellent solubility and water resistance.
CI Acid Black 52, CI Acid Black 11
9 is preferably used.

The reaction between the cationic surfactant and the metal complex hydrochloric acid dye is not particularly limited. For example, an aqueous solution of the cationic surfactant and an aqueous solution of the metal complex hydrochloric acid dye may be mixed at room temperature to 100 ° C.
Then, it can be easily used as a colorant by contact treatment. Since this colorant becomes water-insoluble and is separated, it can be obtained by washing with water and drying.

For the purpose of the present invention, such a manufacturing method is not limited by the spirit of the present invention.

The coloring agent thus obtained is dissolved in an alcohol-soluble resin and an alcohol-based solvent to obtain the black ink composition for writing of the present invention. The content of the coloring agent is 12 to 20% in the ink composition. 40% by weight, preferably 15-30% by weight
It is necessary to contain it in the range of. If the content of the colorant is too large, the viscosity of the ink composition becomes too high, which is not practically preferable. If the content of the colorant is less than 12% by weight, the color density is low, especially when written on glass, transparent plastic, etc. Practically unsatisfactory as black ink.

As the alcohol-soluble resin used in the present invention,
Examples thereof include ketone resin, rosin-modified maleic acid resin, phenol resin, polyvinyl butyral resin, and ceramic resin.

These alcohol-soluble resins may be used alone or in combination of two or more kinds, and it is desirable to contain them in the ink composition in an amount of 1 to 30% by weight, preferably 5 to 20% by weight. .

By containing the alcohol-soluble resin, the adhesive force of the ink to various materials such as paper, wood, glass, stone, plastics, etc. is improved, and the viscosity of the ink can be adjusted. If the content is too large, the viscosity of the ink composition becomes too high, which is not preferable in practice. If the content is too small, the above effect is not remarkable.

The alcoholic solvent used in the present invention has ethanol as a main solvent component, and ethanol is contained in the ink composition in an amount of 40 to 85% by weight, preferably 50 to 50% by weight.
It is desirable to contain it in the range of 80% by weight. When the content of ethanol is low, it is not preferable in terms of safety such as low odor and low toxicity.

Other alcohol solvents include, for example, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t
ert-Butyl alcohol, and monohydric alcohols such as isobutyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol and glycerol; and monomethyl ethers or monoethyl ethers of these polyhydric alcohols. Monoalkyl ether and the like can be used, but 20% by weight or less is desirable from the viewpoint of safety.

In addition, the ink composition of the present invention may optionally contain additives commonly used in alcoholic ink compositions, such as surfactants, preservatives and fragrances.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. All "parts" used below are "parts by weight".

Example 1 30 parts of Sumilan Black WA (metal complex hydrochloric acid dye, CI Acid Black 52, manufactured by Sumitomo Chemical Co., Ltd.) was mixed with 9 parts of water.
An aqueous cationic surfactant solution prepared by dissolving 18 parts of Esocard C / 12 (polyoxyethylene alkyl (coconut) monomethylammonium chloride, manufactured by Lion Akzo Co., Ltd.) in 600 parts of water was added to an aqueous solution of dye dissolved in 00 parts of 40 parts. The mixture was reacted at 30 ° C. for 30 minutes with stirring. The reaction product that becomes insoluble in water and precipitates is separated, washed with water and dried to give a colored product 2.
Obtained 3.6 parts.

15 parts of the obtained colored product, 10 parts of Hirac 110H (ketone resin, manufactured by Hitachi Chemical Co., Ltd.), 65 of ethanol
Parts and 10 parts of isopropanol were dissolved to obtain an ink composition of the present invention.

With the felt pen filled with the ink composition of the present invention, it was possible to write on glass, polyvinyl chloride plate, polyethylene film and the like with good quick-drying property, and the adhesive strength was also good. Further, it was immersed in water for 1 day, but no color elution to water was observed.

Further, the stability test of the ink composition of the present invention was carried out at 0 ° C. for 4 months, but no precipitate was observed at all.

Example 2 30 parts of SPT-Black W-1 (metal complex hydrochloric acid dye, CI Acid Black 119, Hodogaya Chemical Co., Ltd.) was dissolved in 900 parts of water to prepare an aqueous dye solution, and Esocard C / 1.
2 (polyoxyethylene alkyl (coconut) monomethyl ammonium chloride, manufactured by Lion Akzo Co., Ltd.) 22
An aqueous solution of a cationic surfactant in which 400 parts of water was dissolved was added, and the mixture was reacted by stirring at 40 ° C. for 30 minutes. The reaction product that became insoluble in water and precipitated was separated, washed with water and dried to obtain 25.3 parts of a colored product.

20 parts of the colored product obtained, 8 parts of Hirac 110H (ketone resin, manufactured by Hitachi Chemical Co., Ltd.), 62 parts of ethanol,
An ink composition of the present invention was obtained by dissolving 5 parts of n-propanol and 5 parts of benzyl alcohol.

With the felt pen filled with the ink composition of the present invention, it was possible to write on glass, polyvinyl chloride plate, polyethylene film and the like with good quick-drying property, and the adhesive strength was also good. Further, it was immersed in water for 1 day, but no color elution to water was observed.

Further, the stability test of the ink composition of the present invention was carried out at 0 ° C. for 3 months, but no precipitate was observed.

Example 3 30 parts of SPT-Black W-1 (metal complex hydrochloric acid dye, CI Acid Black 119, manufactured by Hodogaya Chemical Co., Ltd.) was dissolved in 900 parts of water in an aqueous dye solution and Esocard C / 1.
2 parts of polyoxyethylene oleyl monomethyl ammonium chloride (manufactured by Lion Akzo Co., Ltd.) 2 in 6 parts of water
Add an aqueous solution of cationic surfactant dissolved in 00 parts,
The reaction was carried out by stirring at 40 ° C. for 30 minutes. The reaction product which became insoluble in water and precipitated was separated, washed with water and dried to give a colored product 28.
I got one copy.

The ink composition of the present invention was prepared by dissolving 15 parts of the obtained colored product, 10 parts of Marquid No. 33 (rosin-modified maleic acid resin, manufactured by Arakawa Chemical Industry Co., Ltd.), 60 parts of ethanol and 15 parts of n-butanol. Obtained.

With the felt pen filled with the ink composition of the present invention, it was possible to write on glass, polyvinyl chloride plate, polyethylene film and the like with good quick-drying property, and the adhesive strength was also good. Further, it was immersed in water for 1 day, but no color elution to water was observed.

Further, the stability test of the ink composition of the present invention was carried out at 0 ° C. for 3 months, but no precipitate was observed.

Comparative Example 1 Nigrosine BR (acid dye, CI Acid Black 2,
An aqueous cationic surfactant solution prepared by dissolving 9 parts of Sanizole C (alkyldimethylbenzyl ammonium chloride, manufactured by Kao Corporation) in 200 parts of water was added to an aqueous dye solution prepared by dissolving 30 parts of Orient Chemical Industry Co., Ltd. in 900 parts of water. The reaction mixture was added and stirred at 40 ° C. for 30 minutes. The reaction product that becomes insoluble in water and precipitates is separated, washed with water and dried to give a colored product 2.
7.2 parts were obtained.

12 parts of the obtained colored product, 10 parts of Hirac 110H (ketone resin, manufactured by Hitachi Chemical Co., Ltd.), 68 of ethanol
Part, and 10 parts of isopropanol were attempted to be dissolved, but they were not completely dissolved and an ink having a sufficient color density was not obtained.

Comparative Example 2 30 parts of Sumilan Black WA (metal complex hydrochloric acid dye, CI Acid Black 52, manufactured by Sumitomo Chemical Co., Ltd.) was added to 4 parts of water.
In an aqueous dye solution dissolved in 00 parts, Sanizole C (alkyl dimethyl benzyl ammonium chloride, Kao Corporation)
A cationic surfactant aqueous solution prepared by dissolving 8 parts of water) in 200 parts of water was added, and the mixture was reacted by stirring at 40 ° C. for 30 minutes.
The reaction product that became insoluble in water and precipitated was separated, washed with water and dried to obtain 26.5 parts of a colored product.

15 parts of the obtained colored product, 10 parts of Hirac 110H (ketone resin, manufactured by Hitachi Chemical Co., Ltd.), 68 of ethanol
Part, and 10 parts of isopropanol were attempted to be dissolved, but they were not completely dissolved and an ink having a sufficient color density was not obtained.

Comparative Example 3 30 parts of Sumilan Black WA (metal complex hydrochloric acid dye, CI Acid Black 52, manufactured by Sumitomo Chemical Co., Ltd.) was added to 4 parts of water.
Cation BB (lauryl trimethyl ammonium chloride, NOF CORPORATION) in an aqueous dye solution dissolved in 00 parts
An aqueous solution of a cationic surfactant prepared by dissolving 35 parts of water in 200 parts of water was added, and the mixture was reacted by stirring at 40 ° C. for 30 minutes. The reaction product that became insoluble in water and precipitated was separated, washed with water and dried to obtain 27.8 parts of a colored product.

15 parts of the obtained colored product, 10 parts of Hirac 110H (ketone resin, manufactured by Hitachi Chemical Co., Ltd.), 68 of ethanol
Parts, and 10 parts of isopropanol were dissolved to obtain an ink composition, but in a stability test at 0 ° C., a precipitate was observed after 1 week.

〔The invention's effect〕

The black ink composition for writing of the present invention is an alcoholic ink composition containing ethanol as a main solvent component, which has improved solubility of a colorant which could not be dissolved to a sufficient color density, and has long-term stability. In addition to being excellent in water resistance and excellent in light resistance of the metal complex hydrochloric acid dye, ethanol is the main solvent unlike the conventional solvents such as xylene, toluene or methyl ethyl ketone, which are concerned about safety. As a component, it can provide highly safe ink and is suitable for writing on a wide range of materials such as glass, wood products, practic, paper, cloth, and stone.

Claims (1)

[Claims] 1. A cationic surfactant represented by the following general formula [1] and C.I. I. Acid Black 52, C.I. I. Acid Black 52: 1, C.I. I. Acid black 10
7, C.I. I. Acid Black 118, C.I. I. Acid Black 119, C.I. I. A black ink composition for writing comprising a colorant obtained by reacting one or more metal complex hydrochloric acid dyes in Acid Black 155, an alcohol-soluble resin, and an alcohol solvent containing ethanol as a main solvent. . (In the formula, X represents a halogen atom; R represents a saturated or unsaturated aliphatic hydrocarbon group having 12 to 18 carbon atoms; and the total number of m and n represents an integer of 2 to 15.)